Casein derivatives and process for the manufacture of the same.



UNITED srn rns (PATENT orrion.

RUDOLF TAMBAGH, or LUZDWI'GSHAFENQON-THE-RHINE, GERMANY, ass'renon TO THE rum or KNOLL AND COMPANY, or LITDWIGSHAFEN-ON-THE-RHINE, ennmnnr.

oAsnm nnnrvn'rrvns, AND raoonss FOR THE MANUFACTURE or THE SAME.

No Drawing.

To all whom it may concern:

Be it known that I, RUDOLF TAMBACH, a subject of the German Emperor, residing at Ludwigshafen-on-the-Rhine, Germany, have invented certain new and useful'Casein Derivatives and Processes for the Manufacture of the Same, of which the following is a specification.

Chlorinated derivatives of casein have hitherto been prepared by treating casein dissolved in the necessary quantity of sodium carbonate solution with chlorin, care being taken, that the hydrochloric acid formed during the reaction is neutralized with solid sodium carbonate, after the solution has become acid. This process is repeated, until a sample of the product shows a sufficiently high percentage of chlorin.

' According to another known method aid of heat, simultaneous oxidation andchlorination of the casein takes place, protially as regards their (Habermann and Ehrenfeld Zeitschm'ft ft'ir Physiclogz'sche Ohemz'e, vol. 32 (1901) pages 470 and 4:71) casein in alkaline solution has been mixed with potassium chlorate, and this solution treated with gaseous hydrochloric acid, until the cake separated out at the beginning of the acid reaction and consequently of the liberation of chlorin has again entered into solution. Fromthe acid liquid thus obtained-the casein chlorid derivative is then separated by means ofwater. The process therefore consists in treating casein with nascent chlorin in the presence of acids. i

I have found, that when casein in alkaline solution is treated. with alkali-hypochlorites or with chlorin in the cold or with the vided that the action of the chlorinating media takes place in the presence of an excess ofalkahyor is interrupted at the comm'encement of the acid reaction. The products obtainable in this manner difl'er essenhysical properties from those obtained by tlie processes hithervtoknown.

The chlorinated derivatives of casein obtained by treatingwith chlorin a solution of casein, for instance in a solution of sodium-carbonate, while taking care that an excess of sodium carbonate is present or by interrupting thdtreat'ment with chlorin at the commencement of'the acid reaction, are

soluble in alkalis, but insoluble in water,

' Specification of Letters Patent.

Patented Sept. 3, 1912.

Application filed March 20, 1908. Serial No. 422,241.

acids and alcohol of various degrees of strength. The products prepared by Habermann and Ehrenfelds method and also those prepared according to thepresent process are soluble in alkalis, and insoluble in water and acids; the absence of sulfur is a feature common to both, and both are soluble in dilute alcohol with the aid of heat. but while the product of Habermann and Ehrenfeld remains in solution, after the addition of concentrated alcohol, the product obtained by the present process is pre cipitated. Moreover, the present process utilizes about 70 per cent. of the casein em ployed, while according to Habermann and Ehrenfeld only about 5 per cent. of the casein employed is converted into the chlorin derivative, if in the process of chlorination the introduction of hydrochloric acid is continued until the real solution of .the casein. The chlorinated and oxidized derivatives of casein are obtained by the present process in the shape of a yellow powder, in which the percent-age of chlorin varies between 2 and 8 'per cent, according to the conditions of working. They are free from sulfur, contain phosphorus and about 12 per cent. of nitrogen.

Example I: kilogram of casein is stirred I soda solution, the solution is then heated with 2 liters of an approximately ten per cent. sodium hypochlorite solution at 75-80 'C. for about 2 hours. After the small quantity of residue has been separated by hydrochloric acid, to precipitate the chlorinated derivatives of casein. The product, when dried, contains about 5 per cent. of chlorin, which cannot be separated by boilinglwith a solution of potassium iodld. Y

xample II: A hot solution (about 70 C.) of 1. kilo-gram of casein in 5 liters of water and 2 liters of a 35% caustic soda solution is treated, with gaseous chlorin, until the formationofa precipitate comfiltration, the'filtrate is treated with strong.

mences. Complete precipitation is produced by'means of mineral acids, and the chlorinated derivative of casein thus produced s filtered off and washed with absolute alcohol and ether. When dried, it contains about 3.5 per cent-.- of chlorin.

:Example III: A warm solution (about 30 C.) of l kilogram of caseinin 10 liters of water and 2 liters of a per cent. caustic soda solution is treated with chlorin gas, until the generation or gas which occurs at first subsides. During the whole time the liquid, in which the chemical reaction takes place, must be kept alkaline. The casein chlorin derivative produced is then separated by means of acid, washed with absolute alcohol and dried. When dried, it contains about 8 er cent. of chlorin, which may besplit o partly by means of potassium-iodid solution.

Example IV 1 kilogram of casein is dissolved in 10 liters of water and 1 liter of a sodium carbonate solution at the temperature of a Water-bath and then treated with chlorin gas at about C. until the solution begins to become acid (as shown by a test samp e). The chlorinated derivatives of casein produced are then separated by means of mineral acids, which product after filtration is Washed with absolute alcohol mamas and ether and dried. When dried it contains about 4t per cent. of chlorin.

][ have found that these chlorinated de-.

nesses.

RUDOLF TAMBACH. Witnesses:

Oswam Kane, Joe. H. Laura. 

